Aqueous dispersions of fluorine-containing polymers

ABSTRACT

Aqueous dispersions of fluorine-containing polymers 
     The aqueous solvent-free dispersions contain polymers of monomers of the formulae (1) and (2) 
     
         H.sub.2 C═CR--COOC.sub.2 H.sub.4 --C.sub.n F.sub.2n+1  (1) 
    
     where R is fluorine, chlorine, hydrogen or methyl and n is from 5 to 18, 
     
         H.sub.2 C═CRX                                          (2) 
    
     where R is hydrogen or methyl and X is a group of the formula C 6  H 5 , CO 2  CH 2  C 6  H 5 , CO 2  C 2  H 4  C 6  H 5 , CN, CO 2  CH 2  C 6  H 4  Cl, CO 2  C 6  H 4  --C 1  --C 4  --alkyl, CO 2  C 2  H 2n+1 , where n is from 10 to 22, CONHY, where Y is hydrogen, C 1  -C 4  -alkyl, C 1  -C 4  -hydroxyalkyl, C 1  -C 4  -alkoxy-C 1  -C 4  -alkyl or CO 2  -C 1  -C 20  -alkyl, and one or more emulsifiers of the formula (3) 
     
         C.sub.n F.sub.2n+1 --CR.sup.1 R.sup.2 --CHR.sup.3 --(CH.sub.2).sub.x 
    
      --NR 2  O                                              (3) 
     where R is C 1  -C 4  -alkyl or hydroxyethyl R 1  and R 2  are identical or different and each is C 1  -C 4  -alkyl, hydrogen or fluorine, R 3  is hydrogen or C 1  -C 4  -alkyl, x is 1, 2 or 3 and n is from 3 to 9, and/or of the formula (4) 
     
         R.sup.1 R.sup.2 R.sup.3 NO                                 (4) 
    
     where R 1  and R 2  are identical or different and each is C 1  -C 4  -alkyl or hydrogen and R 3  is C 8  -C 18  -alkyl. 
     The dispersions are used as water and oil repellants for textiles.

The invention relates to aqueous, solvent-free fluorinecontaining dispersions, a process for preparing them, and their use for the fluorochemical treatment of textiles such as carpets, upholsteries and others in order to confer water and oil resistance on them. Polymers having perfluoroalkyl groups are suitable substances for rendering textiles or carpets both hydrophobic and oleophobic, as described for example in EP 345 552, EP 332 141, EP 73364 and US 3,356,628. These polymers are preferably used for technical reasons in the form of aqueous and ideally solvent-free dispersions.

However, the preparation of aqueous, solvent-free dispersions by known emulsion polymerization techniques is difficult, since the perfluoroalkyl monomers are extremely water-insoluble and it is impossible to obtain stable emulsions in water. The addition of organic solvents, for example acetone, to increase the monomer solubility, as described inter alia in U.S. Pat. No. 3,403,122, produces dispersions which are usually coarsely granular and not very stable under storage. For these reasons the perfluoroalkyl monomers are sometimes polymerized in solution, before the polymer obtained is made into a dispersion. This necessarily requires a further operation compared with an emulsion polymerization and, owing to the presence of solvent in the product, has only limited suitability for use. Moreover, the subsequent dispersing of a precipitated fluoropolymer proves expensive in practice.

It has now been found that the use of amine oxide emulsifiers leads to stable aqueous dispersions whose application properties are distinctly superior to those of other systems. The dispersions obtained are notable in particular because they represent stable systems without the addition of organic solvents and in that, owing to the amine oxide emulsifier, they have an almost neutral pH.

The present invention accordingly provides aqueous, solvent-free dispersions of polymers of monomers of the formulae (1) and (2)

    H.sub.2 C═CR--COOC.sub.2 H.sub.4 --C.sub.n F.sub.2n+1  (1)

where R is fluorine, chlorine, hydrogen or methyl and n is from 5 to 18, preferably from 8 to 12,

    H.sub.2 C═CRX                                          (2)

where R is hydrogen or methyl and X is a group of the formula C₆ H₅, CO₂ CH₂ C₆ H₅, CO₂ C₂ H₄ C₆ H₅, CN, CO₂ CH₂ C₆ H₄ Cl, CO₂ C₆ H₄ -C₁ -C₄ -alkyl, CO₂ C_(n) H_(2n+1), where n is from 10 to 22, preferably from 14 to 18, CONHY, where Y is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -hydroxyalkyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl or CO₂ -C₁ -C₂₀ -alkyl, preferably CO₂ -C₂ -C₈ -alkyl, and one or more emulsifiers of the formula (3)

    C.sub.n F.sub.2n+1 --CR.sup.1 R.sup.2 --CHR.sup.3 --(CH.sub.2).sub.x --NR.sub.2 O                                              (3)

where R is C₁ -C₄ -alkyl or hydroxyethyl, R¹ and R² are identical or different and each is C₁ -C₄ -alkyl, hydrogen or fluorine, R³ is hydrogen or C₁ -C₄ -alkyl, x is 1, 2 or 3 and n is from 3 to 9, preferably from 5 to 7, and/or of the formula (4)

    R.sup.1 R.sup.2 R.sup.3 NO                                 (4)

where R¹ and R² are identical or different and each is C₁ -C₄ -alkyl or hydrogen and R³ is C₈ -C₁₈ -alkyl, preferably C₁₀ -C₁₄ -alkyl.

The proportion of fluorine-free comonomer of the formula (2) in the polymers can be up to 50 percent by weight.

The emulsifiers used are preferably compounds of the formula (3) where R¹ and R³ are each hydrogen, R² is fluorine, R is C₁ -C₄ -alkyl or CH₂ CH₂ OH, n is from 3 to 9 and x is from 1 to 3, which can be present mixed with up to 30 percent by weight, based on the mixture, of a compound of the formula (3) where R¹, R² and R³ are each hydrogen, R is C₁ -C₄ -alkyl or CH₂ CH₂ OH, n is from 3 to 9 and x is from 1 to 3. Suitable emulsifiers of the formula (3) are in particular those compounds where R¹ and R³ are each hydrogen, R² is fluorine, R is methyl or ethyl, n is from 5 to 7 and x is 1 or 2, which can be present mixed with up to 30 percent by weight, based on the mixture, of a compound of the formula (3) where R¹, R² and R³ are each hydrogen, R is methyl or ethyl, n is from 5 to 7 and x is 1 or 2.

The emulsifiers of the formulae (3) and (4) can be used mixed with co-emulsifiers of the formula (5)

    C.sub.n H.sub.2n+1 --C.sub.6 H.sub.4 --O--(C.sub.2 H.sub.4 O).sub.m H (5)

where n is from 4 to 16, preferably from 8 to 10, and m is from 10 to 30, preferably from 18 to 26, and/or coemulsifiers of the formula (6)

    C.sub.n H.sub.2n+1 --O--(C.sub.2 H.sub.4 O).sub.m H        (6)

where n is from 10 to 2%, preferably from 13 to 18, and m is from 4 to 12, preferably from 7 to 9.

To achieve the technical purpose, the emulsifiers of the formulae (3) and (4) can each be used alone or mixed with one another in any desired mixing ratio. For the stability of the dispersions it is advantageous if up to 50 percent by weight of the emulsifiers of the formulae (3) and/or (4) is replaced by one or more co-emulsifiers of the formulae (5) and (6).

The total amount of emulsifier, based on the total amount of monomer, should be 5-30 percent by weight, preferably 10-15 percent by weight.

To prepare the aqueous dispersions of the present invention the preferred procedure is to admix the monomer mixture with the emulsifiers and any co-emulsifiers and add sufficient water as to produce for the dispersions a fluorine content of 10-30 percent by weight, based on the total dispersion, from the fluorine contents of the monomers and the added emulsifiers together. The mixture is in general stirred at 50° C. under nitrogen for 30 minutes and then a water-soluble free radical initiator customary for an emulsion polymerization, for example azodiisobutyramidine dihydrochloride, is added as catalyst. After heating for example to 50°-60° C. for several hours (see Table 1) the dispersion is stirred without further heating until back at room temperature.

The aqueous dispersions of the present invention are suitable for treating textiles made of natural or synthetic fibers, in particular polyamide, polyester, polyacrylonitrile and wool or blends of these fibers. The textile material can be present in any desired form, for example as tow, loose fiber, yarn, knitted fabric or nonwoven but in particular as woven fabric. The aqueous dispersions of the present invention can be applied to the textile material in the as-prepared form. Customarily, however, they are diluted with water to a solids content of 0.1-10% by weight, preferably 1-5% by weight, before use. Application to the textile material to be treated can take the form of spraying, nip padding, slop padding, etc. The amount applied is such that 0.01-1% by weight of fluorine, preferably 0.03-0.2% by weight of fluorine, ends up on the textile material. After application, the textile material is dried at temperatures of up to about 120° C. and is then subjected at temperatures of about 130°-190° C., preferably 140°-180° C., to a heat treatment which customarily takes from about 20 seconds to 5 minutes. While the amine oxides of the formulae (3) and (4) remain stable in the preparation of the aqueous dispersions of the present invention, at the temperatures of above 120° C. necessary for fixing the dispersions on the textile fiber they decompose virtually quantitatively (differential thermal gravimetry), which is particularly beneficial for the oil and water repellancy. Since the decomposition products of the emulsifiers used according to the present invention are largely gaseous, they consequently do not interfere with the application through yellowing which might be caused by secondary reactions of the decomposition products.

The fluorine-containing, aqueous polymer dispersions prepared according to the present invention show excellent oil and water repellant effects in textile finishing not only in respect of washing but also in respect of drycleaning resistance. They can be used as a textile finish either alone or combined with other finishes, such as crosslinkers or softeners.

                                      TABLE 1                                      __________________________________________________________________________     Preparation Examples:                                                                                                         Precipitation                   Example No.                                                                           Fluoro monomer                                                                          Comonomers                                                                               Emulsifiers                                                                             Initiator                                                                            Temp (°C.)                                                                    (% of TM)                       __________________________________________________________________________      1     40 g of AAE                                                                             0.75                                                                              g of ABU                                                                              6 g of B101                                                                             0.4 g of AB                                                                          60    1.3                                             16 g of BA                                                                               2 g of N230                                                                    2 g of X080                                           2     40 g of AAE                                                                             0.75                                                                              g of ABU                                                                              6 g of B101                                                                             0.4 g of AB                                                                          60    0.02                                            14 g of Ba                                                                               2 g of N230                                                          0.96                                                                              g of NH A                                                                             2 g of X080                                           3     40 g of AAE                                                                             0.75                                                                              g of ABU                                                                              6 g of B101                                                                             0.4 g of AB                                                                          60    0.5                                             14 g of BA                                                                               2 g of N230                                                          2.0                                                                               g AA   2 g of X080                                           4     40 g of AAE                                                                             0.75                                                                              g of ABU                                                                              6 g of B101                                                                             0.4 g of AB                                                                          60    0.3                                             14 g of BA                                                                               2 g of N230                                                          2.0                                                                               g of AN                                                                               2 g of X080                                           5     40 g of AAE                                                                             2.0                                                                               g of ABU                                                                              6 g of B101                                                                             0.4 g of AB                                                                          60    1.1                                             15 g of BA                                                                               2 g of N230                                                                    2 g of X080                                           6     40 g of AAE                                                                             0.75                                                                              g of ABU                                                                              6 g of B101                                                                             0.4 g of AB                                                                          60    0.2                                             14 g of BA                                                                               2 g of N230                                                          2.0                                                                               g of IBMA                                                                             2 g of X080                                           7     41.6                                                                              g of AAE                                                                             0.63                                                                              g of ABU                                                                              9 g of B101                                                                             0.7 g of AB                                                                          50    1.2                                             0.4                                                                               g of LA                                                                               4 g of N230                                           8     40 g of AAE                                                                             0.75                                                                              g of ABU                                                                              12                                                                               g of B101                                                                             0.4 g of AB                                                                          60    0.1                                             14 g of BA                                                                     0.96                                                                              g NHMA                                                       9     41.6                                                                              g of AAE                                                                             0.63                                                                              g of ABU                                                                              9 g of B101                                                                             0.7 g of AB                                                                          50    0.5                                             0.96                                                                              g of NHMA                                                                   0.4                                                                               g of LA                                                     10     40 g of AAE                                                                             14 g of BA                                                                               10                                                                               g of DMDA                                                                             0.4 g of AB                                                                          60    0.9                                             0.75                                                                              g of ABU                                                                    0.96                                                                              g of NHMA                                                   11     40 g of AAE                                                                             14 g of BA                                                                               6 g of DMDA                                                                             0.4 g of AB                                                                          60    0.7                                             0.75                                                                              g of ABU                                                                              4 g of B101                                                          0.96                                                                              g of NHMA                                                   12     40 g of AAE                                                                             14 g of BA                                                                               6 g of CC                                                                               0.4 g of AB                                                                          60    0.1                                             0.75                                                                              g of ABU                                                                              4 g of B101                                                          0.96                                                                              g of NHMA                                                   13     40 g of AAE                                                                             10 g of BA                                                                               6 g of B101                                                                             0.4 g of AB                                                                          60    0.1                                             0.75                                                                              g of ABU                                                                              2 g of X080                                                          2.88                                                                              g of NHMA                                                                             2 g of N230                                          14     40 g of AAE                                                                             14 g of BA                                                                               4 g of B101                                                                             0.4 g of AB                                                                          60    0.5                                             0.75                                                                              g of ABU                                                                              6 g of HN1                                                           0.96                                                                              g of NHMA                                                   15     40 g of AAE                                                                             14 g of BA                                                                               4 g of B101                                                                             0.4 g of AB                                                                          60    0.5                                             0.75                                                                              g of ABU                                                                              6 g of HN9                                                           0.96                                                                              g of NHMA                                                   16     40 g of AAE                                                                             10 g of BA                                                                               12                                                                               g of B101                                                                             0.4 g of AB                                                                          60    5.8                                             0.75                                                                              g of ABU                                                                    2.88                                                                              g of NHMA                                                   17     40 g of AAE                                                                             8  g of BA                                                                               12                                                                               g of B101                                                                             0.4 g of AB                                                                          60    0.3                                             0.75                                                                              g of ABU                                                                    0.96                                                                              g of NHMA                                                                   6  g of P-Cl                                                   18     21.6                                                                              g of AAE                                                                             0.63                                                                              g of ABU                                                                              9 g of B101                                                                             0.7 g of AB                                                                          50    0.3                                    20 g of MAE                                                                             0.96                                                                              g of NHMA                                                                   0.4                                                                               g of LA                                                     19     40 g of AAE                                                                             16 g of BA                                                                               6 g of CAT1                                                                             0.4 g of AB                                                                          60    1.1                                             0.75                                                                              g of ABU                                                                              2 g of N230                                                                    2 g of X080                                          20     40 g of AAE                                                                             16 g of BA                                                                               6 g of CAT2                                                                             0.4 g of AB                                                                          60    5.4                                             0.75                                                                              g of ABU                                                                              2 g of N230                                                                    2 g of X080                                          21     40 g of AAE                                                                             16 g of BA                                                                               6 g of CAT3                                                                             0.4 g of AB                                                                          60    1.7                                             0.75                                                                              g of ABU                                                                              2 g of N230                                                                    2 g of X080                                          __________________________________________________________________________      Component 1: 3 g of a 50% strength aqueous solution of highly                  methanoletherified melaminemethylol                                            Component 2: 6 g of a 25% strength aqueous zinc nitrate solution, 1 ml of      60% strength acetic acid                                                       Component 3: 6 g or 12 g of a commercial approximately 25% strength water      repellant ( ® NUVA FH)                                               

Comparative Example 22 contains as emulsifier a compound of the formula

    C.sub.6 F.sub.13 --(CH.sub.2).sub.2 --O--CONH--(CH.sub.2).sub.2 --S--SO.sub.3 Na.

Compared with the emulsifiers to be used according to the present invention, this compound has the disadvantage that it only fully decomposes at temperatures above 250° C. Moreover, the fluorine-containing component 3 can be used only together with a melamine resin and a zinc nitrate solution. This disadvantage disappears with the dispersions prepared according to the present invention.

GM=total monomer, AAE=acrylic acid ethylperfluoroalkyl ester mixture of the approximate composition:

4-6% of C₆ F₁₃ CH₂ CH₂ OCOCH═CH₂

48-58% of C₈ F₁₇ CH₂ CH₂ OCOCH═CH₂

8-13% of C₁₀ F₂₁ CH₂ CH₂ OCOCH═CH₂

2-4% of C₁₂ F₂₅ CH₂ CH₂ OCOCH═CH₂

0.3-1.2% of C₁₄ F₂₉ CH₂ CH₂ OCOCH═CH₂

MAE=methacrylic acid ethylperfluoroalkyl ester mixture 0f the approximate composition:

0-1% of C₆ F₁₃ CH₂ CH₂ OCOC(CH₃)═CH₂

0.4-1.4% of C₈ F₁₇ CH₂ CH₂ OCOC(CH₃)═CH₂

38-42% of C₁₀ F₂₁ CH₂ CH₂ OCOC(CH₃)═CH₂

31-36% of C₁₂ F₂₅ CH₂ CH₂ OCOC(CH₃)═CH₂

12-16% of C₁₄ F₂₉ CH₂ CH₂ OCOC(CH₃)═CH₂

2-6% of C₁₆ F₃₃ CH₂ CH₂ OCOC(CH₃)═CH₂

BA=benzyl acrylate; ABU=acryloylbutylurethane;

NHMA=N-hydroxymethylacrylamide;

IBMA=N-hydroxymethylacrylamide isobutyl ether;

LA=lauryl acrylate; AA=acrylamide; AN=acrylonitrile;

P-Cl=para-chlorobenzyl acrylate;

AB=azodiisobutyramidine dihydrochloride;

B101=C₅ F₁₁ CHFCH₂ CH₂ N(CH₃)₂ O;

N230=nonylphenol condensed with 23 EO;

X080=isotridecyl alcohol condensed with 8 EO;

DMDA=N,N-dimethyldodecylamine N-oxide;

CC=cocoalkyldimethylamine N-oxide;

HN1═C₈₋₁₀ H₁₇₋₂₁ N(CH₃)₂ O;

HN9═C₁₂ H₂₅ N(CH₃ (C₄ H₉)O;

CAT1═C_(n) F_(2n+1) CH₂ CH₂ OCOCH₂ CH₂ N(C₄ H₉)₂ xHCl where n=4-12;

CAT2═C₆₋₁₂ F₁₃₋₂₅ (C₂ H₄ O)₁₆ H;

CAT3═C₆ F₁₃ CH₂ CH₂ SSO₃ Na.

Application testing of the aqueous fluorine-containing polymer dispersions and comparative examples:

The dispersions of Examples 1, 2 and 18 of the present invention were tested plus for comparison the dispersions 19 to 22.

The finishing liquors were made up in such a way that their fluorine contents were constant and that a predetermined wet pickup after squeezing would produce a defined fluorine add-on on the fabrics to be treated.

The test results in Table 2 were produced with a polyamide taffeta fabric by way of example. In each case the test was carried out as follows:

The polyamide taffeta fabric to be tested was impregnated, squeezed off to a residual level of 50%, dried at 110° C. and heated at 150° C. for three minutes to effect condensation. The fluorine add-on on the fabrics was thus about 0.05% by weight or 0.1% by weight.

The water and oil repellancy effects measured on this polyamide taffeta fabric are summarized below in Table 2.

                                      TABLE 2                                      __________________________________________________________________________     Test        Example 18                                                                           Example 1                                                                            Example 2                                                                            Example 19                                                                           Example 20                                                                           Example 21                                                                           Example                        __________________________________________________________________________                                                     22                             Fluorine add-on (ppm)                                                                      500                                                                               1000                                                                              500                                                                               1000                                                                              500                                                                               1000                                                                              500                                                                               1000                                                                              500                                                                               1000                                                                              500                                                                               1000                                                                              500                                                                               1000                        Water repellancy                                                               Spray test (AATCC 22)                                                          At the beginning                                                                           100                                                                                100                                                                               90                                                                                100                                                                              100                                                                                100                                                                               70                                                                                100                                                                               90                                                                                90                                                                               70  80                                                                               100                                                                                100                        after 3×  washing at                                                                  80                                                                                100                                                                               50                                                                                50                                                                                70                                                                                70                                                                                0   0                                                                                0   0                                                                               0    0                                                                                70                                                                                80                         60° C.                                                                  after 3×  drycleaning                                                                100                                                                                100                                                                              -- -- -- -- -- -- -- -- -- -- 100                                                                                100                        Oil repellancy                                                                 Test in accordance                                                             with AATCC 118                                                                 At the beginning                                                                            6   6                                                                                5   6                                                                                6   7                                                                                5   6                                                                                5   6                                                                               2    3                                                                                5   6                         after 3×  washing at                                                                  2   4                                                                                1   2                                                                                4   4                                                                                0   1                                                                                0   0                                                                               0    0                                                                                3   4                         60° C.                                                                  after 3×  drycleaning                                                                 6   6                                                                               -- -- -- -- -- -- -- -- -- --  5   6                         __________________________________________________________________________ 

What is claimed is:
 1. An aqueous, solvent-free dispersion of a polymer comprising monomers of the formulae (1) and (2)

    H.sub.2 C═CR--COOC.sub.2 H.sub.4 --C.sub.n F.sub.2n+1  ( 1)

where R is fluorine, chlorine, hydrogen or methyl and n is from 5 to 18,

    H.sub.2 C═CRX                                          (2)

wherein R is hydrogen or methyl and X is a group of the formula C₆ H₅, CO₂ CH₂ C₆ H₅, CO₂ C₂ H₄ C₆ H₅, CN, CO₂ CH₂ C₆ H₄ Cl, CO₂ C₆ H₄ -C₁ -C₄ -alkyl, CO₂ C_(n) H_(2n+1), where n is from 10 to 22, CONHY, where Y is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -hydroxyalkyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl or CO₂ -C₁ -C₂₀ -alkyl, and one or more emulsifiers of the formula (3)

    C.sub.n F.sub.2n+1 --CR.sup.1 R.sup.2 --CHR.sup.3 --(CH.sub.2).sub.x --NR.sub.2 O                                              (3)

where R is C₁ -C₄ -alkyl or hydroxyethyl, R¹ and R² are identical or different and each is C₁ -C₄ -alkyl, hydrogen or fluorine, R³ is hydrogen or C₁ -C₄ -alkyl, x is 1, 2 or 3, and n is from 3 to 9, or of the formula (4)

    R.sup.1 R.sup.2 R.sup.3 NO                                 (4)

wherein R¹ and R² are identical or different and each is C₁ -C₄ -alkyl or hydrogen and R³ is C₈ -C₁₈ -alkyl or a mixture of one or more emulsifiers of the formulae (3) an (4).
 2. A dispersion as claimed in claim 1, containing as emulsifier only a compound of the formula (3).
 3. A dispersion as claimed in claim 1, containing a compound of the formula (3)

    C.sub.n F.sub.2n+1 --CR.sup.1 R.sup.2 --CHR.sup.3 --(CH.sub.2).sub.x --NR.sub.2 O                                              (3)

where R¹ and R³ are each hydrogen, R² is fluorine, R is C₁ -C₄ -alkyl or CH₂ CH₂ OH, n is from 3 to 9 and x is from 1 to 3, optionally mixed with up to 30 percent by weight, based on the mixture, of a compound of the formula (3) where R¹, R² and R³ are each hydrogen, R is C₁ -C₄ -alkyl or CH₂ CH₂ OH, n is from 3 to 9 and x is from 1 to 3, as emulsifier.
 4. A dispersion as claimed in claim 1, containing a compound of the formula (3)

    C.sub.n F.sub.2n+1 --CR.sup.1 R.sup.2 --CHR.sup.3 --(CH.sub.2).sub.x --RN.sub.2 O                                              (3)

where R¹ and R³ are each hydrogen, R² is fluorine, R is methyl or ethyl, n is from 5 to 7 and x is 1 or 2, optionally mixed with up to 30 percent by weight, based on he mixture of a compound of the formula (3) where R¹, R² and R³ are each hydrogen, R is methyl or ethyl, n is from 5 to 7 and x is 1 or 2, as emulsifier.
 5. A dispersion as claimed in claim 1, wherein an amount up to 50 percent by weight of the emulsifier of the formula (3) or (4) are replaced by one or more co-emulsifiers of the formula (5)

    C.sub.n H.sub.2n+1 --C.sub.6 H.sub.4 --)--(C.sub.2 H.sub.4 O).sub.m H (5)

where n is from 4 to 16, and m is from 10 to 30, or of the formula (6)

    C.sub.n H.sub.2n+1 --O--(C.sub.2 H.sub.4 O).sub.m H        (6)

where n is from 10 to 20, and m is from 4 to 12 or a mixture of one or more emulsifiers of the formula (3), (5) and (6).
 6. A dispersion as claimed in claim 1, wherein the total amount of emulsifier, based on a total amount of monomer, is 5-30 percent by weight.
 7. A dispersion according to claim 1 having a fluorine content, based on the total dispersion, of 10-30 percent by weight.
 8. A process for producing a dispersion as claimed in claim 1, which comprises dispersing monomers of the formulae (1) and (2) in the presence of emulsifiers of the formulae (3), (4), (5) or (6) or a mixture of one or more emulsifiers of the formulae (3), (4), (5) and (6) in water and reacting to produce said dispersion.
 9. A water and oil repellant for textiles comprising a dispersion as claimed in claim
 1. 10. A dispersion as claimed in claim 1, wherein n from formula (1) is from 8 to
 12. 11. A dispersion as claimed in claim 1, wherein n from formula (2) is from 14 to 18 and Y is CO₂ -C₂ -C₈ -alkyl.
 12. A dispersion as claimed in claim 1, wherein n from formula (3) is from 5 to
 7. 13. A dispersion as claimed in claim 1, wherein R³ from formula (4) is C₁₀ -C₁₄ -alkyl.
 14. A dispersion as claimed in claim 5, wherein n form formula (5) is from 8 to 10 and m from formula (5) is from 18 to
 26. 15. A dispersion as claimed in claim 5, wherein n from formula (6) is from 13 to 18 and m from formula (6) is from 7 to
 9. 16. A dispersion as claimed in claim 6, wherein the total amount of the emulsifier, based on the total amount weight of the monomer is 10-15% by weight.
 17. A dispersion as claimed in claim 1, wherein the emulsifier of formula III has R¹ and R³ each as hydrogen, R² is fluorine, R is C₁ -C₄ -alkyl or CH₂ CH₂ OH, n is from 3 to 9 and x is from 1 to
 3. 18. The process as claimed in claim 8, further requiring the process to be initiated by a water-soluble free radical initiator.
 19. The process as claimed in claim 18, wherein said free radical initiator is azodiisobutyramidine dihydrochloride.
 20. The water and oil repellant as claimed in claim 9, wherein said dispersion is diluted with water to a solids content of 0.1-10% by weight. 